Photocatalytic oxidation of Reactive Red 195 by bimetallic Fe-Co catalyst: Statistical modeling and optimization via Box-Behnken design.

Response surface methodology (RSM) is an effective tool for process optimization with multi-complex operational factors. The present work aims to model and optimize the photocatalytic oxidation (PCO) parameters of Reactive Red 195 (RR195) dye decoloration with the SiO2-supported Fe-Co catalyst (FCS) derived from a novel catalyst synthesis method, fluidized-bed crystallization (FBC) process, using Box-Behnken design (BBD) as the RSM statistical model. The Fe-Co@SiO2 catalyst was successfully fabricated using the FBC process, and it showed good catalytic activity and performance toward the degradation of RR195. The extent of the effects of pH, H2O2 dosage (HD), catalyst loading (CL), and operating time (t) on the decoloration of RR195 was studied. Hence, the order of variable significance follows the sequence: pH > t > CL > HD. pH has the most significant effect among the variables for RR195 decoloration. The decoloration efficiency predicted by the BBD model was 88.3% under the optimized operation conditions of initial pH of 3.15, 0.76 mM H2O2, 1.18 g L-1 FCS and 59.4 min of operating time. The actual decoloration efficiency was very close to the predicted value indicating that BBD can efficiently be utilized to optimize RR195 degradation with FCS under the PCO system.

Recovering struvite from livestock wastewater by fluidized-bed homogeneous crystallization as a pre-treatment process to sludge co-digestion.

Livestock wastewater can contain high levels of phosphates and trace amounts of various ionic species harming the environment and human health. These ions can be successfully removed from livestock effluent and recovered in a non-toxic crystal form via crystallization. The fluidized bed homogeneous crystallization (FBHC) technology is a cutting-edge pretreatment method that removes phosphate and ammonium by crystallizing struvite. The findings demonstrated a 37% removal for ammonium solutions alone, 38% with copper, 35% with zinc, and 33% when copper and zinc were present, while the crystallization efficiency was achieved at 35%, 33% with copper, 28% with zinc, and 26% with copper and zinc. For phosphate-containing solutions, 95% was removed, 81% with copper, 96% with zinc, and 88% with copper and zinc. Similarly, crystallization efficiency was attained at 87%, 60% with copper, 94% with zinc, and 81% when copper and zinc were combined with phosphates. For ammonium solutions, copper and zinc reduced the removal and crystallization efficiency at constant pH and increased at increasing pH. For phosphate solutions, the removal and crystallization efficiencies increased at increasing pH. However, zinc ions resulted in the highest removal, and crystallization efficiency for phosphate solutions was attained. Based on SEM, EDS, XRD, and XPS analyses, the peaks revealed the presence of struvite in the form of magnesium ammonium phosphate.

Kinetics and thermodynamics of organo-sulfur-compound desorption from saturated neutral activated alumina.

Desulfurization of liquid fuels mitigates the amount of noxious sulfur oxides and particulates released during fuel combustion. Existing literature on oxidative-adsorptive desulfurization technologies focus on sulfur-in-fuel removal by various materials, but very little information is presented about their desorption kinetics and thermodynamics. Herein, we report for the first time, the mechanism of sulfur desorption from neutral activated alumina saturated with dibenzothiophene sulfone. Batch experiments were conducted to examine the effects of agitation rate, desorption temperature, sulfur content, and eluent type on sulfur desorption efficiencies. Results show enhanced desorption capacities at higher agitation rate, desorption temperature, and initial sulfur content. Desorption efficiency and capacity of acetone were found to be remarkably superior to ethanol, acetone:ethanol (1:1), and acetone:isopropanol (1:1). Desorption kinetics reveal excellent fit of the nonlinear pseudo-second-order equation on desorption data, indicating chemisorption as the rate-determining step. Results of the thermodynamics study show the spontaneous (ΔG° ≤ -2.08 kJ mol-1) and endothermic (ΔH° = 32.35 kJ mol-1) nature of sulfur desorption using acetone as eluent. Maximum regeneration efficiency was attained at 93% after washing the spent adsorbent with acetone followed by oven-drying. Scanning electron microscopy, Fourier transform infrared, and X-ray diffraction spectroscopy analyses reveal the intact and undamaged structure of neutral activated alumina even after adsorbent regeneration. Overall, the present work demonstrates the viability of neutral activated alumina as an efficient and reusable adsorbent for the removal of sulfur compounds from liquid fossil fuels.

Competitive effect of copper and nickel recovery with carbonate in the fluidized-bed homogeneous granulation process.

With the rapid growth of the world's informatics innovation, printed circuit boards (PCBs) processing produces wastewaters with copper and nickel ions. This study aims to remove and recover copper and nickel ions from synthetic PCB wastewater using a fluidized-bed homogeneous granulation process (FBHGP). FBHGP is an advanced green technology that removes copper and nickel and transforms the sludge into a hard granule. The impacts on the removal and granulation of copper and nickel of the initial operating pH, molar ratio (MR) of precipitant to metal, and precipitant flow rate have been evaluated. The highest copper removal was attained at 97% at pH of 6.5 and 98% copper removal at an MR of 2.0 and 10 mL·min-1. A 93% copper granulation was achieved at the same pH, while a 94% copper granulation was also achieved at the same MR and precipitant flow rate. At a pH of 7.5, 85% nickel removal and 74% granulation were attained for a nickel. At an MR of 1.75, 82% and 74% were the highest removal and granulation. While at 25 mL·min-1, the highest removal was 83%, and 73% nickel granulation was achieved. Copper has been successfully recovered from synthetic PCB wastewater using FBHGP. At the same time, nickel needs a multi-step FBR, which is more suitable for the recovery of nickel under the same conditions applied during the same period.

Electrochemically-driven regeneration of iron (II) enhances Fenton abatement of pesticide cartap.

Cartap is a carbamate insecticide intended to protect crops such as rice, tea, and sugarcane. Cartap in the environment presents a serious threat to non-target organisms through direct exposure or via biomagnification. Electro-assisted Fenton technology taps the potential of Fenton reagents to degrade cartap. Electrochemical reduction of iron accelerates catalyst regeneration. Cartap degradation was first investigated by varying reaction pH, as well as the initial H2O2 and Fe2+ dosage, followed by optimization studies using central composite design. Parametric results indicate the highest cartap removal of 98.10% was achieved at 1.6 pH, 3.0 mM Fe2+, and 40 mM H2O2 at I = 1.0 A and t = 30 min. These results notoriously surpass conventional Fenton that only achieved 53.8% cartap removal under similar conditions. The hybridization of Fenton process through electrochemical regeneration enhances removal and increases degradation kinetic up to a pseudo-first-order rate constant value of 21.30 × 10-4 s-1. Effects of coexisting inorganic salts PO43-, NO3-, and Cl- at 1 mM and 10 mM concentrations were investigated. These results demonstrate that Fenton electrification as process intensification alternative can enhance the performance and competitiveness of conventional Fenton by ensuring higher availability of iron catalyst while minimizing sludge production.

Investigation and disinfection of bacteria and fungi in sports fitness center.

This study investigated the air quality improvement in terms of bacterial and fungal contamination in an exercise room of a fitness center under normal operating conditions. Environmental conditions including air conditioning, ventilation, moisture, CO2, particulate matters, and total number of users were also recorded. In addition, fungal and bacterial load were assessed and disinfection on sports equipment surface was also examined. Background bacteria and fungi densities in bioaerosols were in the range of 249 ± 65 to 812 ± 111 CFU/m3 and 226 ± 39 to 837 ± 838 CFU/m3 in the exercise room of the fitness center and 370 ± 86 to 953 ± 136 CFU/m3 and 465 ± 108 to 1734 ± 580 CFU/m3 in the outdoor air, respectively. Chlorine dioxide and weak acid hypochlorous water aerosols could remove both bacteria and fungi much better than water scrubbing. Contact time of 15 min was sufficient to control both bacteria and fungi to comply with the official air quality standards. User density and carbon dioxide deteriorated both bacteria and fungi disinfection performance whereas temperature was only statistically significant on fungi disinfection. Other factors including relative humidity, airflow velocity, and particulate matters did not have any statistically significant effect on microbial inactivation. Apart from bioaerosol disinfection, inactivation of microorganisms on surfaces of sports equipment was also conducted using chlorine dioxide, zinc oxide, weak acid hypochlorous water, and commercial disinfectant. The surfaces of bicycle handle, dumbbell, and sit-up bench were found to be contaminated with bacteria. Overall bacterial load was 390 to 3720 CFU/cm2 with Escherichia coli specifically 550 to 1080 CFU/cm2. Chlorine dioxide and zinc oxide were noticeably better than weak acid hypochlorous water and commercial disinfectant in terms of bacteria inactivation whereas all tested disinfectants had comparable effectiveness on E. coli disinfection. Targeted microorganisms on the sports equipment surface were sufficiently inactivated within 2 min after the application of disinfectant.

Disinfection efficiency of hospital infectious disease wards with chlorine dioxide and hypochlorous acid.

The disinfection efficiencies of two chemical disinfectants, chlorine dioxide and weak acid hypochlorous water (WAHW), were examined in the soiled room and dishwashing room of a hospital infectious disease ward in Taiwan. The investigations were conducted in two seasons, namely winter and summer, in order to examine the correlation between the bioaerosol concentration and the environmental factors. In addition, a single-daily disinfection mode (SM) and a twice-daily disinfection mode (TM) were applied in this study. The results showed that the bacteria and fungi colony counts were strongly correlated with the temperature. Both disinfectants reduced the bacteria and fungi concentrations in the considered rooms. However, of the two disinfectants, the ClO2 showed a stronger disinfection effect than the WAHW. It means that when using ClO2 as the disinfectant, the disinfection efficiency of the TM treatment mode is significantly better than that of the SM treatment mode. But, when using WAHW as the disinfectant, no significant difference is found between the disinfection efficiencies of the two methods. Overall, the results showed that the application of ClO2 twice daily provided the most effective means of satisfying the Taiwan EPA guidelines for the indoor air quality of hospital medical wards.

Cartap removal from simulated water matrices by fluidized-bed Fenton process: optimization of process parameters.

Cartap is a thiocarbamate pesticide widely-used to protect rice crops, one of the most mass-produced cereals worldwide. Effluents containing cartap pose serious environment and health risks due to the acute toxicity of this emerging contaminant. This work evaluates the capabilities of the Fenton process to efficiently remove cartap from water matrices. Process parameters such as hydrogen peroxide dosage, ferrous ion concentration and operating pH were optimized using Box-Behnken design. Results showed complete cartap removal with Fenton oxidation in a fluidized-bed reactor while eliminating sludge generation during treatment. Fluidized-bed Fenton process had improved reduction in chemical oxygen demand and total organic carbon due to the contribution of heterogeneous Fenton catalysis to the overall degradation of cartap species compared to conventional Fenton in a batch reactor. Furthermore, competitive reactions and scavenging effects in complex natural water matrices were simulated with the use of inorganic ions such as nitrate, chloride, and phosphate. Results demonstrated the detrimental effect of phosphate ions on Fenton oxidation due to the precipitation of soluble catalysts as iron phosphates, which stops the catalytic Fenton cycle and thus the production of oxidants for contaminant degradation.

Synthesis and catalytic utilization of bimetallic systems for wastewater remediation: A review.

The environment is affected by agricultural, domestic, and industrial activities that lead to drastic problems such as global warming and wastewater generation. Wastewater pollution is of public concern, making the treatment of persistent pollutants in water and wastewater highly imperative. Several conventional treatment technologies (physicochemical processes, biological degradation, and oxidative processes) have been applied to water and wastewater remediation, but each has numerous limitations. To address this issue, treatment using bimetallic systems has been extensively studied. This study reviews existing research on various synthesis methods for the preparation of bimetallic catalysts and their catalytic application to the treatment of organic (dyes, phenol and its derivatives, and chlorinated organic compounds) and inorganic pollutants (nitrate and hexavalent chromium) from water and wastewater. The reaction mechanisms, removal efficiencies, operating conditions, and research progress are also presented. The results reveal that Fe-based bimetallic catalysts are one of the most efficient heterogeneous catalysts for the treatment of organic and inorganic contamination. Furthermore, the roles and performances of bimetallic catalysts in the removal of these environmental contaminants are different.

Theoretical design of two-dimensional carbon nitrides.

The study of two-dimensional (2D) materials has attracted considerable attention owing to their unique but fascinating properties. Here we systematically explored 2D carbon nitride monolayer sheets via the particle swarm optimization algorithm in combination with density functional theory. As a result of structural searches, four carbon nitride monolayers are predicted with stable stoichiometries of C5N2, C2N, C3N2and CN. These predicted structures are semiconductors with an optimal band gap for solar cell application as indicated in our electronic simulations. Our current results also reveal the high tensile strengths of the predicted structures compared to known porous carbon nitride monolayer sheets. This work may provide a route for the design of 2D candidates in the application of photovoltaic materials.

Beyond carbon capture towards resource recovery and utilization: fluidized-bed homogeneous granulation of calcium carbonate from captured CO2.

Atmospheric carbon dioxide (CO2) imbalance due to anthropogenic emissions has direct impact in climate change. Recent advancements in the mitigation of industrial CO2 emissions have been brought about by a paradigm shift from mere CO2 capture onto various adsorbents to CO2 conversion into high value products. The present study proposes a system which involves the conversion of CO2 into high purity, low moisture, compact and large CaCO3 solids through homogeneous granulation in a fluidized-bed reactor (FBR). In the present study, synthetic solutions of potassium carbonate (K2CO3) and calcium hydroxide (Ca(OH)2) were used as sources of carbonate and precipitant, respectively. The effects of the degree of supersaturation (S) as chemical loading and influx flow rate (QT) as hydraulic loading on CaCO3 granulation efficiency were investigated. In the study, S was varied from 10.2 to 10.8 and QT from 40 to 80 mL min-1 while the operating pH and calcium-is-to-carbonate molar ratio ([Ca2+]/[CO32-]) were set at 10 ± 0.2 and 1.50, respectively. Results showed that carbonate ions end product distribution had a highest carbonate granulation efficiency at [Carbonate]G of 95-96% using S of 10.6 and QT of 60 mL min-1. Characterization of the granules confirmed high purity calcium carbonate. Overall, the transformation of industrial CO2 emissions into a valuable solid product can be a significant move towards the mitigation of climate change from anthropogenic emissions.

Effect of calcination time of a quadruple-element doped titania nanoparticles in the photodegradation of gaseous formaldehyde under blue light irradiation.

The photocatalytic degradation of gaseous formaldehyde using Ag/F/N/W-doped titanium dioxide was examined. The photocatalytic reaction was conducted using photocatalysts immobilized on glass tubular reactors illuminated under blue LED lights. Factors affecting gaseous formaldehyde degradation such as photocatalyst's calcination time and dosage, initial formaldehyde concentration, light intensity and operating temperature were studied. Results show that the photocatalytic degradation rate increases with pollutant concentration indicating no mass transfer limitations within the formaldehyde concentration range used. The photodegradation of the formaldehyde using catalyst calcined for 5 h reached ∼88%. The photocatalyst concentration giving the highest degradation rate is found to be 0.10 gL-1. Which means that upon increasing the concentration of the immobilized photocatalysts will increase its thickness and it may not increase the number of the photo-induced particles. On the other hand, increasing light intensity and operating temperature increased the photocatalytic degradation of gaseous formaldehyde. The maximum light intensity and operating temperature were measured at 25 Wm-2 and 40 °C, respectively. Langmuir-Hinshelwood kinetic type model was used to describe the photocatalytic reaction. The photocatalytic degradation behavior of gaseous formaldehyde on the modified photocatalyst follows a pseudo-first order rate equation based on a Langmuir-Hinshelwood kinetic type model.

Doping TiO2 with CuSO4 enhances visible light photocatalytic activity for organic pollutant degradation.

Photocatalysis is one of the most promising advanced oxidation processes due to the capability of solid catalyst to continuously produce oxidant species under light irradiation. The use of conventional UV lamps is high cost intensive, which undermines the possible implementation in developing countries. Visible light active photocatalysts can overcome these challenges and find a market opportunity for competitive technology implementation. This work proposes the synthesis of visible light active catalyst following a facile sol-gel synthesis that introduces CuSO4 as dopant in TiO2. Results present complete abatement of methylene blue in 120 min of treatment under 50 mW cm-2 of blue light (λ = 450 nm), while commercial P25 TiO2 presented null abatement under identical conditions. Synthesis parameters including dopant level and calcination temperature allowed defining optimum synthesis conditions based on material characteristics modification and catalytic activity enhancement. A doping level of 0.21 mol% CuSO4 was identified as optimum condition to enable visible light photocatalysis of doped TiO2 catalysts calcined at 300 °C. Finally, operational parameters were evaluated defining a wide range of pH operation under 3.0 g L-1 of catalyst dose to treat up to 20 g L-1 of highly recalcitrant phenothiazine dye. These optimum conditions allowed complete dye removal under visible light after 120 min of treatment.

Fluoride network and circular economy as potential model for sustainable development-A review.

Fluorine is the most reactive elements among the halogen group and commonly and ubiquitously occurs as fluoride in nature. The industrial processes produce fluoride by-products causing the increase of unwanted environmental levels and consequently posing risk on human and environmental health worldwide. This review gives a fundamental understanding of fluoride networks in the industrial processes, in the geological and hydrological transport, and in the biological sphere. Numerous biological pathways of fluoride also increase the risk of exposure. Literature shows that various environmental levels of fluoride due to its chemical characteristics cause bioaccumulation resulting in health deterioration among organisms. These problems are aggravated by emitted fluoride in the air and wastewater streams. Moreover, the current waste disposal dependent on incineration and landfilling superpose to the problem. In our analysis, the fluoride material flow model still follows a linear economy and reuse economy to some extent. This flow model spoils resources with high economic potential and worsens environmental problems. Thus, we intend a shift from the conventional linear economy to a circular economy with the revival of three-dimensional objectives of sustainable development. Linkages between key dimensions of the circular economy to stimulate momentum for perpetual sustainable development are proposed to gain economic, environmental and social benefits.

Enhanced recovery of aluminum from wastewater using a fluidized bed homogeneously dispersed granular reactor.

The recovery of aluminum from wastewater is one of the main environmental issues that need to be addressed in the aluminum finishing industry. A new technique of converting a soft slurry into hard granules using the homogeneous granulation process in the fluidized-bed reactor (FBR) can respond to this problem. It is a better method of remediation than producing a slurry containing 70% water. This study deals with the recovery of aluminum from aqueous solutions using Fluidized-bed homogeneous granulation process (FBHGP) without seeds. The hydraulic operating conditions were optimized using Box-Behnken Design (BBD) to attain the optimum aluminum removal (AR%) and granulation ratio (GR%). Optimum values of AR% = 98.8% and GR% = 96.9% were attained at the following conditions: influent aluminum concentration, 334.1 mg L-1; precipitant pH, 10.4; molar ratio (MR) of precipitant to metal [OH-]in/[Al3+]in, 2.5. The characteristics of the granules were comparable with those of orthorhombic structure of aluminum oxide (Al2.66O4). FBHGP was proven to be effective as dictated by the reaction mechanism in the recovery of aluminum from aluminum-rich aqueous solutions.

Leisure activity participation in relation to alcohol purchasing and consumption in adolescence.

BACKGROUND: Building upon the socioecological perspective, this study examines prospective associations linking leisure activity participation with alcohol purchasing and consumption in early adolescence. METHODS: A total of 1763 seventh graders (age 12-13 years) were recruited from middle schools in urban Taiwan via multi-stage sampling and followed-up 1.5 years later during ninth grade. Information about leisure activities, covariates (i.e., gender, puberty development, family structure, parental educational attainment, monthly allowance, peer drinking, and childhood alcohol experience), and two outcome variables (i.e., alcohol purchasing and drinking behaviors) was gathered via web-based self-administered questionnaires. Data concerning alcohol outlets and recreational resource for each community district were retrieved from official statistics and commercial sources. Two-level hierarchical generalized linear models were used to evaluate association estimates. FINDINGS: Five percent of ninth graders ever purchased alcohol and nearly one in seven drank alcohol on three or more occasions (i.e., occasional drinking) in the past year. Sports, unstructured, and organized leisure activities were not linked with illegal alcohol purchasing when community contexts were statistically adjusted; a higher community on-premised alcohol outlet density increased alcohol purchasing by 94% (95% CI = 1.24-3.06). In contrast, unstructured leisure activity participation at 7th grade predicted occasional drinking (adjusted Odds Ratio [aOR] = 5.52; 95% CI = 3.13-9.74). Sports participation was associated with reduced risk of occasional drinking in the communities with high unregulated alcohol outlets (aOR for interaction = 0.58; P < .001). CONCLUSION: Our research provides insights to differential roles of leisure activity participation in shaping adolescents' commercial alcohol access and occasional drinking. Macro-social contexts should be considered in the efforts to reduce underage drinking problems through leisure activities.

Improvement of indoor air quality in pet shop using gaseous chlorine dioxide.

Many studies have shown that pet shops have a high concentration of bioaerosols. Thus, effective disinfection protocols are essential to protect the pet shop staff and visitors to the store. The present study examines the effectiveness of gaseous chlorine dioxide (ClO2) fogging in minimizing the residual bacteria and fungi levels in a typical pet shop in Taiwan consisting of a commodity area, a lodging area, and a grooming area. This investigation uses three disinfection modes (DMs) according to different disinfection periods, namely once every hour (1DM), once every 2 h (2DM), and once every 3 h (3DM). The bacteria and fungi concentrations are measured before and after disinfection treatment, and the effectiveness of each disinfection mode is evaluated using standard statistical techniques. To assess the effect of the environmental factors on the disinfection efficiency, measurements are taken of temperature, relative humidity, airflow velocity, the carbon dioxide concentration, the PM1, PM2.5, PM7, PM10, and TSP level at each sampling locations. The results reveal that the effectiveness of the three disinfection modes depends on both the environmental parameters and the use of the three areas (e.g., commodity, lodging, or grooming). Hence, the choice of disinfection method should be adjusted accordingly. For all three disinfection modes, a faster air velocity is beneficial in spreading the disinfectant throughout the indoor space and improving the disinfection performance. Overall, the results presented in this study confirm that gaseous chlorine dioxide disinfection improves the air quality in the pet shop interior, and thus beneficial in safeguarding the health of the pet shop staff and visitors.

Effect of catalyst calcination temperature in the visible light photocatalytic oxidation of gaseous formaldehyde by multi-element doped titanium dioxide.

The present study investigates the influence of calcination temperature on the properties and photoactivity of multi-element doped TiO2. The photocatalysts were prepared by incorporating silver (Ag), fluorine (F), nitrogen (N), and tungsten (W) into the TiO2 structure via the sol-gel method. Spectroscopic techniques were used to elucidate the correlation between the structural and optical properties of the doped photocatalyst and its photoactivity. XRD results showed that the mean crystallite size increased for undoped photocatalysts and decreased for the doped photocatalysts when calcination was done at higher temperatures. UV-Vis spectra showed that the absorption cut-off wavelength shifted towards the visible light region for the as-synthesized photocatalysts and band gap narrowing was attributed to multi-element doping and calcination. FTIR spectra results showed the shifting of OH-bending absorption bands towards increasing wave numbers. The activity of the photocatalysts was evaluated in terms of gaseous formaldehyde removal under visible light irradiation. The highest photocatalytic removal of gaseous formaldehyde was found at 88%. The study confirms the effectiveness of multi-element doped TiO2 to remove gaseous formaldehyde in air by visible light photocatalysis and the results have a lot of potential to extend the application to other organic air contaminants.